Basic mono- and bisazo compounds

ABSTRACT

The invention relates to basic mono- and bisazo compounds according to formula (I) 
                         
wherein all substituents are defined as in Claim 1, their production, their use as dyestuffs as well as material dyed with these dyestuffs.

The invention relates to basic mono- and bisazo compounds, salts thereofand mixtures of these compounds, which may be in internal or external,salt form. They are suitable for use as dyestuffs.

U.S. Pat. No. 4,764,175 provides monoazo and disazo compounds having a1-hydroxy-5,6-, 7- or 8-substituted 1,3,5-triazinylamino-3- or 4sulfonic acid coupling component radical.

However there is still a need to produce dyes having improvedproperties. Surprisingly, it was found that dyes according to formula(I) as shown below of the present application have those desiredproperties.

According to the invention there are provided compounds of formula (I)

wherein

-   -   R₁ is H; C₁–C₄alkyl or C₁–C₄alkyl monosubstituted by —OH,    -   X₁ and X₂ independently of each other are an aliphatic,        cycloaliphatic, aromatic or heterocyclic amino group, and at        least one amino group comprises a protonatable nitrogen atom or        a quaternary ammonium group, and being an aliphatic,        cycloaliphatic, aromatic or heterocyclic mono(C₁₋₄alkyl)-amino        group, the C₁₋₄alkyl-group being unsubstituted or        monosubstituted by halogen, C₁₋₄alkoxy, C₁₋₄alkyl, phenyl or        hydroxy; an aliphatic, cycloaliphatic, aromatic or heterocyclic        di(C₁₋₄alkyl)-amino group, the C₁₋₄alkyl-groups being        independently unsubstituted or monosubstituted by halogen,        C₁₋₄alkyl, C₁₋₄alkoxy, phenyl or hydroxy; a C₅₋₆cycloalkylamino        group, the cycloalkyl group being unsubstituted or substituted        by one or two C₁₋₂alkyl groups; a phenylamino group, the phenyl        ring being unsubstituted or substituted by one or two groups        selected from halogen, C₁₋₄alkyl, C₁₋₄alkoxy, hydroxy and        phenoxy; or a 5- or 6-membered ring containing one or two hetero        atoms, in addition to N, O or S, which heterocyclic ring is        unsubstituted or substituted by one or two C₁₋₄alkyl groups; or        a group Z, where Z is independently selected from

where

-   -   p is 0 or an integer 1, 2 or 3,    -   each R₂ is independently H; unsubstituted C₁₋₄alkyl or C₁₋₄alkyl        monosubstituted by hydroxy, halogen, cyano or C₁₋₄alkoxy,    -   each R₃ and R₄ is independently H; unsubstituted C₁₋₆alkyl;        C₂₋₆alkyl monosubstituted by hydroxy or cyano; phenyl or        phenyl-C₁₋₄alkyl, where the phenyl ring of the latter two groups        is unsubstituted or substituted by one to three groups selected        from chlorine, C₁₋₄alkyl, C₁₋₄alkoxy, unsubstituted        C₅₋₆cycloalkyl or C₅₋₆cycloalkyl substituted by one to three        C₁₋₄alkyl groups, or a pyridinium ring, or    -   R₃ and R₄ together with the nitrogen atom to which they are        attached, form a 5- or 6-membered ring containing one to three        hetero atoms (in addition to N, one or two further N, O or S),        which heterocyclic ring is unsubstituted or substituted by one        or two C₁₋₄alkyl groups,    -   each R₅ and R₆ has independently one of significances of R₃ and        R₄, except hydrogen,    -   R₇ is C₁₋₄alkyl or benzyl with the exception that R₇ is not        benzyl when R₅ and R₆ have one of the cyclic significations of        R₃ and R₄ or    -   R₅, R₆ and R₇ together with the nitrogen atom to which they are        attached, form a pyridinium ring which is unsubstituted or        substituted by one or two methyl groups,    -   Q₁ is C₂₋₈alkylene; branched C₂₋₈alkylene; C₂₋₆alkylene        substituted by one or two hydroxy groups;        C₁₋₆alkylene-1,3-phenylene; or C₁₋₆alkylene-1,4-phenylene,    -   Q₂ is C₂₋₈alkylene; branched C₂₋₈alkylene; C₃₋₆alkylene        substituted by one or two hydroxy groups;        C₁₋₁₆alkylene-1,3-phenylene; C₁₋₆alkylene-1,4-phenylene;        1,3-phenylene or 1,4-phenylene,    -   Q₃ is C₂₋₈alkylene,    -   R₈ is H; unsubstituted C₁₋₆alkyl or C₁₋₆alkyl monosubstituted by        hydroxy, cyano, chlorine or phenyl,    -   R₉ is unsubstituted C₁₋₆alkyl or C₁₋₆alkyl monosubstituted by        hydroxy, cyano or chlorine, and    -   An^(θ) is a non-chromophoric anion,    -   E is NH or a direct bond,    -   m is 0 or 1, and if m is 1 the phenyl group is substituted meta        or para,    -   n is 1 or 2 with the provisos that    -   (i) when n is 1 then        -   DK is a radical of formula (a)

-   -   -    wherein            -   R₁₀ is SO₂—Y or —O—Y, where Y is a C₂₋₄-alkenyl group or                a C₂₋₄alkyl group which is optionally substituted by                —CN, —OH, —OSO₃H, halogen or —NR₁₁R₁₂, wherein R₁₁, and                R₁₂ are independently from one another H, C₁₋₄alkyl or                substituted C₁₋₄alkyl, or R₁₁ and R₁₂ together with the                nitrogen atom to which they are attached, form a 5- or                6-membered ring containing one to three hetero atoms (in                addition to N, one or two further N, O or S), which                heterocyclic ring is unsubstituted or substituted by one                or two C₁₋₄alkyl groups preferably,            -   R′₁₀ and R″₁₀ are independently from one another H;                C₁₋₂alkyl; OC₁₋₂alkyl; —SO₃H; —OH or —CN;        -   or DK is a radical of formula (b)

-   -   -    wherein            -   R₁₃ is H; C₁₋₄alkyl; substituted C₁₋₄alkyl; O—C₁₋₄alkyl;                substituted O—C₁₋₄alkyl; —SO₃H; —OH; —CN; —COOR₁₁;                —NR₁₁R₁₂ or halogen, wherein R₁₁ and R₁₂ have the same                meanings as defined above,            -   R₁₄ and R₁₅ have the same definition as R₁₃ with                exception of hydrogen,            -   wherein at least one of the R₁₃, R₁₄ or R₁₅ is —SO₃H;        -   or DK can be a bicyclic ringsystem wherein each ring is            independently from each other a 5- or 6- membered ring and            the bicyclic ringsystem is not substituted by further azo            groups and

    -   (ii) when n is 2 then        -   DK is a divalent radical B,        -   as well as their salts and/or mixtures thereof.

The compounds can be in internal or external salt form.

Any alkyl or alkylene present is linear or branched unless indicated tothe contrary. In any hydroxy- or alkoxy-substituted alkyl or alkylenegroup, which is linked to a nitrogen atom, the hydroxy or alkoxy groupis bound to a carbon atom other than to the C₁-atom. In any alkylenegroup substituted by two hydroxy groups, the hydroxy groups are bound todifferent carbon atoms.

It is preferred that the substituted triazinyl radical is attached tothe naphthol radical at the 6 or 7 position.

If m is 1 the preferred substitution of the phenylene group of the[—N(R₁)—C(O)-E-phenylene-]-group is meta.

It is also preferred that the sulphonic acid group is attached at the3-position of the naphthol radical.

When DK is a bicyclic ringsystem then each ring can comprise one or moreheteroatom, preferably N, O and/or S. Each ring can be aromatic oraliphatic. Each ring can be substituted.

Any alkyl as R₁ preferably contains 1 or 2 carbon atoms, and is morepreferably methyl. Any alkyl monosubstituted by hydroxy is preferablylinear or branched C₁₋₃alkyl.

R₁ is preferably R_(1a), where each R_(1a) is independently hydrogen;methyl; ethyl or 2-hydroxy-ethyl.

Where X₁ or X₂ is an aliphatic amino group, such group is preferably amono(C₁₋₄alkyl)- or di(C₁₋₄alkyl)-amino group in which each alkyl groupis independently unsubstituted or monosubstituted by halogen(particularly chlorine or bromine), C₁₋₄alkoxy, phenyl or hydroxy, ofwhich substituents hydroxy is most preferred. Any cycloaliphatic aminogroup as X₁ or X₂ is preferably a C₅₋₆cycloalkyl-amino group in whichthe cycloalkyl group is unsubstituted or substituted by one or twoC₁₋₂alkyl groups.

Where X₁ or X₂ is an aromatic amino group, such group is preferably aphenylamino group in which the phenyl ring is unsubstituted orsubstituted by one or two groups selected from halogen (more preferablychlorine), C₁₋₄alkyl, C₁₋₄alkoxy, hydroxy and phenoxy.

Where X₁ or X₂ is a heterocyclic amino group, it is preferably asaturated 5- or 6-membered ring containing one or two hetero atoms (thatis in addition to N, O or S), which heterocyclic ring is unsubstitutedor substituted by one or two C₁₋₄alkyl groups. More preferably it is apiperidino- or morpholino-group.

Any unsubstituted C₁₋₆alkyl group as R₃ or R₄ is preferably methyl orethyl. Any substituted C₂₋₆alkyl group as R₃ or R₄ is preferably ethylor propyl monosubstituted by cyano or hydroxy with the substituent inthe 2- or 3-position.

Any phenyl as R₃ or R₄ is preferably unsubstituted. Any phenylalkylgroup is preferably benzyl, the phenyl ring of which is preferablyunsubstituted. Any cycloalkyl as R₃ or R₄ is preferably cyclohexyl; anyalkylsubstituted cycloalkyl is preferably cyclohexyl substituted by oneto three methyl groups.

R₃ or R₄ are preferably R_(3a) or R_(4a), where each R_(3a) or R_(4a) isindependently hydrogen; unsubstituted C₁₋₄alkyl; linearhydroxy-C₂₋₃alkyl; phenyl; benzyl or a pyridinium ring.

More preferably, R₃ or R₄ are R_(3b) or R_(4b), where each R_(3b) orR_(4b) is independently hydrogen; unsubstituted C₁₋₄alkyl; 2-hydroxethylor a pyridinium ring.

Most preferably, R₃ and R₄ are R_(3c) and R_(4c) respectively, whereeach R_(3c) and R_(4c), is independently hydrogen; methyl or ethyl.

It is particularly preferred that R₃ and R₄ having a non-cyclicsignificance are identical groups.

R₅ and R₆ are preferably R_(5a) and R_(6a) respectively, where eachR_(5a) and R_(6a) is independently unsubstituted C₁₋₄alkyl; linearhydroxy-C₂₋₃alkyl or benzoyl, or R_(5a) and R_(6a) together with thenitrogen to which they are attached form a piperidine-, morpholine-,piperazine- or N-methyl-piperazine-ring.

More preferably, R₅ and R₆ are R_(5b) and R_(6b) respectively where eachR_(5b) and R_(6b) is independently unsubstituted C₁₋₄alkyl or2-hydroxy-ethyl.

Any alkyl as R₇ is preferably methyl or ethyl, especially methyl.

In a preferred embodiment of the invention, Z above has the meaningZ_(a), wherein each Z_(a) is independently a group selected from

in which

-   -   p′ is 0 or 1,    -   R_(2b) is H; methyl or 2-hydroxyethyl,    -   Q_(1b) is unsubstituted C₂₋₆alkylene; monohydroxy-substituted        C₃₋₄alkylene; —(CH₂)₁₋₄-1,3-phenylene; —(CH₂)₁₋₄-1,4-phenylene;        1,3-phenylene or 1,4-phenylene,    -   each Q_(2b) and Q_(3b) is a linear C₂₋₆alkylene group,    -   each R_(3b) and R_(4b) is independently H; unsubstituted        C₁₋₄alkyl or 2-hydroxy-ethyl, or a pyridinium ring,    -   each R_(5b) and R_(6b) is independently unsubstituted C₁₋₄alkyl        or 2-hydroxy-ethyl,    -   R_(7b) is C₁₋₄alkyl or benzyl or    -   R_(5b), R_(6b) and R_(7b) together with the nitrogen to which        they are attached form a pyridinium ring which is unsubstituted        or substituted by one or two methyl groups,    -   R_(8b) is H; methyl; ethyl or 2-hydroxyethyl,    -   R_(9b) is methyl; ethyl or 2-hydroxyethyl,    -   R₁₀ is in position 4, and    -   An^(θ) is a non-chromophoric anion.

In preferred compounds of the invention R₁₀ is a —SO₂—Y or —O—Y radical,wherein Y is a C₂₋₄-alkyl group which is monosubstituted by —Cl, —OH or—OSO₃H.

In preferred compounds of the invention R₁₀ is in position 4.

In further preferred compounds of the invention R₁₀ is a —SO₂—Y or —O—Yradical, wherein Y is a C₂₋₄-alkyl group which is monosubstituted by—NR₁₁R₁₂, wherein R₁₁, and R₁₂ together with the nitrogen atom to whichthey are attached, form a 5- or 6-membered ring containing one to threehetero atoms (in addition to N, one or two further N or O), whichheterocyclic ring is unsubstituted.

In further preferred compounds of the invention R₁₃ is H; —CH₃ or —OCH₃.

In further preferred compounds of the invention R₁₄ and R₁₅ areindependently from one another —CH₃; —CH₂CH₃; —OCH₃; —OCH₂CH₃ or —SO₃H.

Preferred bicyclic ringsystems have the following formulae (c)–(i)

wherein R₁₆, R₁₇ and R₁₈ are independently from each other H; —SO₃H;—OH; —NR₁₁R₁₂, wherein R₁₁ and R₁₂ have the same meanings as definedabove;

wherein R₁₉ and R₂₀ are independently from each other H; —OH; halogen;C₁₋₂alkyl or O—C₁₋₂alkyl;

wherein

-   -   R₂₁ and R₂₂ are independently of one another are H; C₁₋₄-alkyl;        phenyl or a substituted phenyl group having 1 to 5 substituents        selected from the group consisting of C₁₋₄-alkyl, C₁₋₄-alkoxy,        halogen, nitro, cyano, hydroxyl, CF₃, CONH₂,        CONH(C₅₋₆-cycloalkyl), CON(C₁₋₄-alkyl)₂, CONH(C, ₁₋₄)-alkyl,        COO(C, ₁₋₄)-alkyl, COO(C₅₋₆-cycloalkyl) and CONH(phenyl),    -   R₂₃ is H; a trifluoromethyl group; a halogen atom; C₁₋₄-alkyl;        C₁₋₄-alkoxy; a nitro or a cyano group    -   R₁₉ is as defined above;

-   -   wherein R₂₄ is H; methyl; methoxy; ethoxy; chloro or bromo;

-   -   wherein R₂₅ and R₂₆ are independently from each other H;        C₁₋₄alkyl or substituted C₁₋₄alkyl, R₁₉ is as defined above;

-   -   wherein A is S or O and R₁₉ is as defined above;

-   -   wherein A is S or O and R₁₉ is as defined above.        as well as their salts and mixtures thereof.

Preferably the —N═N— group is in formula (h) and (i) in thepara-position.

In further preferred compounds of the present invention, when n is 2 andB is one of the following divalent radicals

wherein each T is independently from one another a direct bond; aC₁₋₄alkylene group; a substituted C₁₋₄alkylene group; a C₂₋₄alkenylenegroup or a substituted C₂₋₄alkenylene group, V is one of the followingradicals

-   -   each R₁ and each R₁₉ and each T has the meanings as defined        above.

Especially preferred compounds according to the present invention havethe following formula

wherein DK is one of the radicals (a) to (i) as defined abovewherein

-   -   R₁₀ is SO₂Y or —O—Y wherein Y is a C₂₋₄ alkyl group which is        substituted by —OH or Y is a C₂₋₄-alkyl group which is        monosubstituted by —NR₁₁R₁₂, wherein R₁₁ and R₁₂ together with        the nitrogen atom to which they are attached, form a 5- or        6-membered ring containing one or two hetero atoms (in addition        to N, one further N or O), which heterocyclic ring is        unsubstituted.    -   R′₁₀ and R″₁₀ are independently from one another H; C₁₋₂alkyl or        OC₁₋₂alkyl,    -   R₁₁ and R₁₂ independently from each other are H; —CH₃ or        —CH₂CH₃,    -   R₁₃ is H; —CH₃ or OCH₃,    -   R₁₄ and R₁₅ are independently from each other are —CH₃; —CH₂CH₃;        —OCH₃; —OCH₂CH₃ or —SO₃H,    -   R₁₆, R₁₇ and R₁₈ are independently from each other H; —NH₂; —OH        or —SO₃H,    -   R₁₉ and R₂₀ are independently from each other H; —CH₃ or —OCH₃,    -   R₂₁ and R₂₂ are independently from each other H; —CH₃ or        —CH₂CH₃,    -   R₂₃ is H; —CH₃ or —CH₂CH₃,    -   R₂₄ is H; —CH₃ or —OCH₃,    -   R₂₅ and R₂₆ are independently from each other H; —CH₃ or        —CH₂CH₃,    -   X₁ and X₂ are independently from each other a group Z_(a) as        defined above.

Further especially preferred compounds according to the presentinvention have the following formula

wherein DK is a divalent radical B which can be chosen from the groupconsisting of

where V is one of the following radicals

each R₁ and each R₁₉ has the meanings as defined above and wherein eachT is independently from one another a direct bond; a C₁₋₄alkylene group;a substituted C₁₋₄alkylene group; a C₂₋₄alkenylene group or asubstituted C₂₋₄alkenylene group, as defined above, and X₁ and X₂ areindependently from each other a group Z_(a) as defined above.

The present invention further provides a process for the preparation ofcompounds of formula (I) comprising reacting the diazonium salt of anamine of formula (II),DK—NH₂  (II)in which DK is as above defined and preferably being so positioned asabove defined, so as to give a preferred compound of formula (I) asabove disclosed, with a compound of formula (III),

in which R₁, X₁, and X₂ are as above defined.

When DK is B, the mole concentration of compound (III) has to be atleast twice the mole concentration of compound (II).

Diazotisation and coupling may be effected in accordance withconventional methods. The coupling reaction advantageously is carriedout in an aqueous reaction medium in a temperature range of from 0–60°C., preferably at 20–50° C., and in a pH range of from 3 to 9,preferably at pH 4 to 6. All temperatures are given in degrees Celsius.

The reaction mixtures comprising compounds of formula (I) thus obtainedmay be converted into stable liquid formulations with improved long termstability by desalting by ultra filtration.

The compounds of formula (I) thus obtained may be isolated in accordancewith known methods.

The compounds of formula (I) containing free basic groups may beconverted wholly or in part into water-soluble salts by reacting withany inorganic or organic acids for example with lactic acid, or aceticacid, or formic acid, or with hydrochloric acid, or with sulfuric acid.

The starting compounds, the amines of formula (II), are either known ormay be prepared in accordance with known methods from available startingmaterials. The compounds of formula (III) may be prepared by step-wisereplacement of the chlorine atoms of cyanuric chloride whereby in afirst and second step, cyanuric chloride is reacted with a diamine offormulae (IV) and (V) (as hereinafter defined), respectively,

in which R_(2b) is as above defined and Q and X have the followingmeanings: Q may have any of the meanings of Q₁, Q₂ or Q₃ above; and Xhas the meaning of X₁.

In the case where identical diamino groups have to be introduced, thisfirst and second step may be combined into one step. Suitably, thesingle step is carried out at temperatures of from 0–30° C. andpreferably at pH 4–6.

Where different diamino groups have to be introduced, suitably, thediamine showing the higher selectivity with respect to the condensationreaction is introduced in the first step at a temperature of preferably0–20° C. more preferably 0–5° C. Both condensation steps may be carriedout using the conventional reaction medium where the upper limit of pHis 7. The second step is preferably carried out at 10–40° C., morepreferably 12–30° C.

The final third step, the condensation with the aminonaphthol component,is carried out at elevated temperatures in the range of 60–100° C. andat pH 2–3.

The starting compounds of formulae (IV) and (V) are either known or maybe prepared in accordance with known methods from available startingmaterials.

The compounds according to the invention, in acid addition salt form orquaternary ammonium salt form, may be used for dyeing cationic dyeablematerials such as: homo- or mixed-polymers of acrylonitrile, acidmodified polyester or polyamide; wool; leather including low affinityvegetable-tanned leather; cotton; bast fibers such as hemp, flax, sisal,jute, coir and straw; regenerated cellulose fibers, glass or glassproducts comprising glass fibers; and substrates comprising cellulosefor example paper and cotton. They may also be used for printing fibers,filaments and textiles comprising any of the above mentioned materialsin accordance with known methods. Printing may be effected byimpregnation of the material to be printed with a suitable printingpaste comprising one or more compounds of the present invention. Thetype of printing paste employed, may vary depending on the material tobe printed. Choice of a suitable commercially available printing pasteor production of a suitable paste, is routine for one skilled in theart. Alternatively the compounds of the present invention may be used inthe preparation of inks suitable for example for jet printing, inaccordance with conventional methods.

Most preferably, the dyestuffs are used for dyeing or printing of papere.g., sized or unsized, wood-free or wood-containing paper orpaper-based products such as cardboard. They may be used in continuousdyeing in the stock, dyeing in the size press, in a conventional dippingor surface coloring process. The dyeing and printing of paper iseffected by known methods.

The dyeings and prints and particularly those obtained on paper, showgood fastness properties.

The compounds of formula (I) may be converted into dyeing preparations.Processing into stable liquid, preferably aqueous, or solid (granulatedor powder form) dyeing preparations may take place in a generally knownmanner. Advantageously suitable liquid dyeing preparations may be madeby dissolving the dyestuff in suitable solvents such as mineral acids ororganic acids, e.g., hydrochloric acid, sulphuric acid, phosphoric acid,formic acid, acetic acid, lactic acid, glycolic acid, citric acid andmethanesulphonic acid. Furthermore formamide, dimethylformamide, urea,glycols and ethers thereof, dextrin or addition products of boric acidwith sorbit may be used together with water, optionally adding anassistant, e.g. a stabilizer. Such preparations may be obtained, forexample, as described in French patent specification No. 1,572,030.

The compounds of formula (I) (in the corresponding salt form) have goodsolubility especially in cold water. Owing to their high substantivitythe compounds of the present invention exhaust practicallyquantitatively and show a good build-up power. They can be added to thestock directly, i.e. without previously dissolving, as either a drypowder or granulate, without reducing the brilliance or the yield ofcolor. They can also be used in soft water without loss of yield. Theydo not mottle when applied on paper, are not inclined to give two-sideddyeing on paper and are practically insensitive to filler or pHvariations. They operate over a broad pH range, in the range of from pH3 to 10. When producing sized or unsized paper, the wastewater isessentially colorless. This feature, which is extremely important froman environmental viewpoint, when compared with similar known dyes, showsa marked improvement. A sized paper dyeing when compared with thecorresponding unsized paper dyeing does not show any decrease instrength.

The paper dyeings or printings made with the compounds according to theinvention are clear and brilliant and have good light fastness. Onexposure to light for a long time, the shade of the dyeing fades tone intone. They show very good wet fastness properties; being fast to water,milk, fruit juice, sweetened mineral water, tonic water, soap and sodiumchloride solution, urine etc. Furthermore, they have good alcoholfastness properties. The wet fastness properties are improved comparedto known dyes showing otherwise similar properties. They do not exhibita tendency towards two-sidedness.

Paper dyed or printed with the compounds of the present invention can bebleached either oxidatively or reductively, a feature, which isimportant for the recycling of waste paper and old paper products.

The compounds of the present invention may also be used to dye papercontaining wood-pulp where even dyeings, having good fastness propertiesare obtained. Furthermore, they may be used for the production of coatedpaper in accordance with known methods. Preferably when coating, asuitable filler, for example kaolin, is employed in order to give aone-side coated paper.

The compounds of the present invention are also suitable for dyeing incombination with other dyes for example other cationic or anionic dyes.The compatibility of the compounds of the present invention when used asa dye in mixtures with other commercially available dyes, may bedetermined according to conventional methods. The thus obtained dyeingshave good fastness properties.

The invention yet further provides use of a compound of the presentinvention for dyeing or printing any of the abovementioned substrates.

The invention further provides a substrate, which has been dyed orprinted with a compound of the present invention. The substrate may beselected from any of the above mentioned substrates. A preferredsubstrate is a substrate comprising cellulose such as cotton or paper orpaper based product.

The following examples further serve to illustrate the invention. In theExamples all parts and all percentages are by weight or volume, and thetemperatures given are in degrees Celsius, unless indicated to thecontrary.

EXAMPLE 1

168.5 parts 4-(2-hydroxyethoxy)-aniline are mixed with 1760 parts ofwater and 293 parts of a 30% solution of hydrochloric acid and arediazotized at 0–5° C. during 1 hour with 286.2 parts of a 4 n solutionof sodium nitrite. During 1 hour the reaction mixture is then pumped to4803 parts of an aqueous solution containing 534.2 parts of a couplingcomponent of the following formula:

During the coupling reaction a pH of 4.5–5 is kept by the addition of a30% solution of sodium hydroxide. The reaction mixture is stirred atroom temperature and pH 4.5–5 for additional 10–14 hours. After risingthe pH value to 8.2, the precipitated dyestuff is filtered off andwashed with 2000 parts of a 5% solution of sodium bicarbonate, 1000parts of a 2% solution of sodium bicarbonate and 2000 parts of a 1%solution of sodium bicarbonate. 2043.1 parts dyestuff presscake of thefollowing formula are obtained (titer ca. 31.4%):

λ_(max)=512 nm in 1% acetic acid)

EXAMPLE 1a

33.5 parts of the dyestuff presscake from example 1 are dried at 80° C.in vacuum over night and are milled to obtain 11.5 parts of a dyestuffpowder. It dyes sized and unsized paper in scarlet shades. The obtainedfastnesses are excellent.

EXAMPLE 1b

300 parts of the dyestuff presscake from example 1 are added at 60–65°C. to a mixture of 100 parts of formic acid and 600 parts of water andare stirred for additional 30 min. 16 parts of Hyflo-Supercel(filtration auxiliary) are added at 60–65° C. and after 10 min stirringthe mixture is filtered. 1000 parts of a long term stable liquiddyestuff formulation are obtained. It dyes sized or unsized paper inscarlet shades. The obtained fastnesses are excellent.

TABLE 1 (Examples 2–108) In an analogous manner as described in Examples1, 1a and 1b using the appropriate starting material, further compoundsof formula (I) are produced. The compounds have the formula (Ia)

in which the symbols have the meaning given in the following table. No.DK X Shade 2

orange 3

scarlet 4

scarlet 5

scarlet 6

scarlet 7

scarlet 8

red 9

red 10

scarlet 11

scarlet 12

scarlet 13

scarlet 14

scarlet 15

scarlet 16

scarlet 17

scarlet 18

scarlet 19

scarlet 20

scarlet 21

scarlet 22

scarlet 23

scarlet 24

scarlet 25

scarlet 26

scarlet 27

scarlet 28

scarlet 29

scarlet 30

scarlet 31

scarlet 32

violet 33

red 34

red 35

red 36

red 37

red 38

violet 39

violet 40

scarlet 41

violet 42

red 43

red 44

red 45

red 46

red 47

red 48

violet 49

violet 50

scarlet 51

scarlet 52

red 53

red 54

scarlet 55

scarlet 56

red 57

red 58

violet 59

violet 60

scarlet 61

scarlet 62

red 63

red 64

orange 65

orange 66

orange 67

orange 68

scarlet 69

scarlet 70

scarlet 71

scarlet 72

scarlet 73

scarlet 74

scarlet 75

scarlet 76

scarlet 78

scarlet 79

scarlet 80

red 81

scarlet 82

scarlet 83

orange 84

scarlet 85

scarlet 86

scarlet 87

scarlet 88

scarlet 89

scarlet 90

scarlet 91

scarlet 92

scarlet 93

scarlet 94

scarlet 95

scarlet 96

scarlet 97

scarlet 98

scarlet 99

scarlet 100

scarlet 101

scarlet 102

scarlet 103

scarlet 104

scarlet 105

scarlet 106

scarlet 107

scarlet 108

scarlet

EXAMPLE 109

61.3 parts 4-(2-hydroxyethoxy)-aniline are mixed with 640 parts of waterand 106.5 parts of a 30% solution of hydrochloric acid and diazotized at0–5° C. during 1 hour with 102.4 parts of a 4 n solution of sodiumnitrite. During 1 hour the reaction mixture is pumped to 1560 parts ofan aqueous solution containing 228.4 parts of a coupling component ofthe following formula:

During the coupling reaction a pH of 4.5–5 is kept by the addition of a15% solution of sodium carbonate. The reaction mixture is stirred atroom temperature and at pH 4.5–5 for additional 10–14 hours. Afteradjusting the pH value to 4.0, ca. 800 parts of sodium chloride areadded in portions. The precipitated dyestuff is filtered off to a yieldof 692.5 parts dyestuff presscake. After drying for 12 hours at 80° C.429 parts of a dyestuff of the following formula are obtained(λ_(max)=513 nm in 1% acetic acid):

It dyes sized or unsized paper in scarlet shades. The obtainedfastnesses are excellent.

TABLE 2 (Examples 110–160) In an analogous manner as described inExample 109 using the appropriate starting material, further compoundsof formula (I) are produced. The compounds have the formula (Ib)

in which the symbols have the meaning given in the following table. No.DK X₁ X₂ Shade 110

red 111

red 112

red 113

violet 114

violet 115

scarlet 116

red 117

violet 118

orange 119

scarlet 120

scarlet 121

scarlet 122

*NH₂

scarlet 123

*HN—CH₃

scarlet 124

scarlet 125

scarlet 126

scarlet 127

scarlet 128

scarlet 129

scarlet 130

scarlet 131

scarlet 132

scarlet 133

scarlet 134

*HN—CH₃

scarlet 135

scarlet 136

*NH₂

scarlet 137

*HN—CH₃

scarlet 138

scarlet 139

scarlet 139

scarlet 140

scarlet 141

scarlet 142

scarlet 143

scarlet 144

scarlet 145

scarlet 146

scarlet 147

scarlet 148

scarlet 149

scarlet 150

scarlet 151

scarlet 152

scarlet 153

scarlet 154

scarlet 155

scarlet 156

scarlet 157

scarlet 158

scarlet 159

scarlet 160

scarlet

EXAMPLE 161

12.2 parts 1,2 bis(4-aminophenoxy)ethane are mixed with 250 parts ofwater and 40 parts of a 30% solution of hydrochloric acid and arediazotized at 0–5° C. during 1 hour with 25.7 parts of a 4 n solution ofsodium nitrite. During 1 hour, the reaction mixture is pumped to 405parts of an aqueous solution containing 50.9 parts of a couplingcomponent of the following formula:

During the coupling reaction a pH of 4.5–5 is kept by the addition of a15% solution of sodium carbonate. The reaction mixture is stirred atroom temperature and pH 4.5–5 for additional 10–14 hours. Theprecipitated dyestuff is filtered off to yield 241.7 parts dyestuffpresscake. After drying for 12 h at 80° C. 83.3 parts of a dyestuff ofthe following formula are obtained (λ_(max)=556 nm in 1% acetic acid):

It dyes sized and unsized paper in red shades. The obtained fastnessproperties are excellent.

TABLE 3 (Examples 162–180) In an analogous manner as described inExample 161 using the appropriate starting material, further compoundsof formula (I) are produced. The compounds have the formula (Ic)

No. DK′ X Shade 162

red 163

red 164

red 165

red 166

red 167

orange 168

orange 169

orange 170

orange 171

scarlet 172

scarlet 173

scarlet 174

scarlet 175

scarlet 176

scarlet 177

scarlet 178

scarlet 179

scarlet 180

scarlet

EXAMPLE 181

11.7 parts 1-Dimethylamino-2-(4-aminophenoxy)-ethane are mixed with 150parts of water and 27 parts of a 30% solution of hydrochloric acid anddiazotized at 0–5° C. during 1 hour with 15.8 parts of a 4 n solution ofsodium nitrite. Afterwards 46.5 parts of a coupling component of thefollowing formula was added:

During the coupling reaction at room temperature first a pH of 4.0–4.5is kept for 2 hours and then for 12 hours at 5.5–6.0 by the addition of100 parts of a 15% solution of sodium carbonate. The precipitateddyestuff is filtered off to yield 138.6 parts dyestuff presscake. Afterdrying for 12 hours at 60° C. 60.9 parts o a dystuff of the followingformula are obtained (λ_(max)=511 nm in 1% acetic acid):

TABLE 4 (Examples 182–202) In an analogous manner as described inExample 181 using the appropriate starting material, further compoundsof formula (I) are produced. The compounds have the formula

No. DK X Shade 182

red 183

red 184

red 185

red 186

red 187

red 188

red 189

red 190

red 191

red 192

red 193

redishorange 194

redishorange 195

red 196

red 197

red 198

orange 199

red 200

red 201

red 202

red

TABLE 5 (Examples 203–212) In an analogous manner as described in 181using the appropriate starting material, further compounds of formula(I) are produced. The compounds have the formula

No. DK X₁ X₂ Shade 203

red 204

red 205

red 206

red 207

red 208

red 209

blueishred 210

scarlet 211

red 212

red

APPLICATION EXAMPLE A

70 parts chemically bleached sulphite cellulose obtained from pinewoodand 30 parts chemically bleached cellulose obtained from birchwood arebeaten in 2000 parts water in a Hollander. 0.2 parts of the dyestuff ofExample 1a are sprinkled into this pulp. After mixing for 10 min, paperis produced from this pulp. The absorbent paper obtained in this way isdyed a brilliant scarlet red. The wastewater is colorless.

APPLICATION EXAMPLE B

0.2 parts of the dyestuff powder according to Example 1a, were dissolvedin 100 parts hot water and cooled to room temperature. The solution isadded to 100 parts chemically bleached sulphite cellulose which havebeen ground with 2000 parts water in a Hollander. After 15 minutesthorough mixing resin size and aluminium sulphate are added thereto.Paper produced in this way has a brilliant scarlet red nuance andexhibits perfect light and wet fastness.

APPLICATION EXAMPLE C

An absorbent length of unsized paper is drawn at 40–50° C. through adyestuff solution having the following composition:

-   -   0.3 parts of the dyestuff according to Example 1a    -   0.5 parts of starch and    -   99.0 parts of water.

The excess dyestuff solution is squeezed out through two rollers. Thedried length of paper is dyed a brilliant scarlet red shade.

The dyestuffs of Examples 2 to 212 as well as mixtures of Examples1a–212 may also be used for dyeing by a method analogous to that ofApplication Examples A to C. The paper dyeings obtained show goodfastness properties.

APPLICATION EXAMPLE D

0.2 Parts of the dyestuff of Example 1a in acid addition salt form aredissolved in 4000 part of demineralised water at 40° C. 100 Parts of apre-wetted cotton textile substrate are added, and the bath is raised tothe boiling point over 30 minutes and held at the boil for one hour. Anywater, which evaporates during dyeing, is replaced continuously. Thedyed substrate is removed form the bath, and after rinsing and drying, abrilliant scarlet red dyeing is obtained having good light-andwet-fastness properties. The dyestuff exhausts practically totally ontothe fiber, and the wastewater is almost colorless.

In a similar manner as described in Application Example D the dyestuffsaccording to Examples 2–212 as well as mixtures of Examples 1a–212 maybe used for dyeing cotton.

APPLICATION EXAMPLE E

100 parts freshly tanned and neutralized chrome leather are agitated for30 minutes in a vessel with a liquor consisting of 250 parts of water at55° C. and 0.5 parts of the dyestuff of Example 1a in acid addition saltform, and then treated in the same bath for 30 minutes with 2 parts ofan anionic fatty liquor based on sulphonated train oil. The leather isthen dried and prepared in the normal way, giving a leather evenly dyedin a brilliant scarlet red shade.

By a method analogous to that described in Application Example E thedyestuffs according to Examples 2–212 may be used for dyeing leather.

Further vegetable-tanned leathers of low affinity may be dyed using thedyestuffs as described herein in accordance with known methods.

APPLICATION EXAMPLE F

Water is added to a dry pulp in Hollander consisting of 60% (by weight)of mechanical wood pulp and 40% (by weight) of unbleached sulphitecellulose, and the slurry is beaten in order to obtain a dry contentslightly exceeding 2.5% and having a beating degree of 40° SR (degreesSchopper-Riegler). The slurry is then exactly adjusted to a high densitydry content of 2.5% by

adding water. 5 Parts of a 2.5% aqueous solution of the dyestuffaccording to Example 1a are added to 200 parts of the above resultingslurry. The mixture is stirred for about 5 minutes and, after theaddition of 2% (by weight) resin size and then 4% (by weight) alum(based on the dry weight) is further stirred for a few minutes untilhomogeneous. The resulting pulp is diluted with about 500 parts water toa volume of 700 parts and then used for the production of paper sheetsby suction on a sheet former. The resulting paper sheets are dyed abrilliant scarlet red.

By a method analogous to that described in Application Example F any oneof the dyestuffs of Examples 2–212 as well as mixtures of Examples1a–212 may be used instead of that of Example 1a. In all cases, thewaste paper exhibits a substantially low residual dye concentration.

APPLICATION EXAMPLE G

Water is added to a dry pulp in a Hollander consisting of 50% (byweight) of chemically bleached sulphite cellulose obtained from pinewoodand 50% (by weight) of chemically bleached sulphite cellulose obtainedfrom birchwood, and the slurry is ground until a degree of grinding of35° SR is reached. The slurry is then adjusted to a high density drycontent of 2.5% by adding water, and the pH of this suspension isadjusted to 7.10 Parts of a 0.5% aqueous solution of the dyestuffaccording to Example 1a are added to 200 parts of the above resultingslurry, and the mixture is stirred for 5 minutes. The resulting pulp isdiluted with 500 parts water and then used for the production of sheetsby suction on a sheet former. The paper sheets thus obtained have abrilliant scarlet red.

By a method analogous to that described in Application Example G furtherdye mixtures may be used consisting of any one of the dyestuffs ofExamples 2–212. In all cases, paper sheets are formed having a brilliantscarlet red shade.

APPLICATION EXAMPLE H

12.6 parts dyestuff of Example 1 are added dropwise at room temperatureto a stirred mixture of 20.0 parts diethyleneglycole and 67.4 parts ofdemineralized water. The resulting ink exhibits good light- andwaterfastness properties. In a similar manner as described inApplication Example H all the Examples of Table 1 and Table 2 and Table3 and Table 4 and Table 5 may be used.

1. Compounds of formula (I)

wherein R₁ is H; C₁–C₄alkyl or C₁–C₄alkyl monosubstituted by —OH, X₁ andX₂ independently of each other are an aliphatic, cycloaliphatic,aromatic or heterocyclic amino group, and at least one amino groupcomprises a protonatable nitrogen atom or a quaternary ammonium group,and being an aliphatic, cycloaliphatic, aromatic or heterocyclicmono(C₁₋₄alkyl)-amino group, the C₁₋₄alkyl-group being unsubstituted ormonosubstituted by halogen, C₁₋₄alkoxy, C₁₋₄alkyl, phenyl or hydroxy; analiphatic, cycloaliphatic, aromatic or heterocyclic di(C₁₋₄alkyl)-aminogroup, the C₁₋₄alkyl-groups being independently unsubstituted ormonosubstituted by halogen, C₁₋₄alkyl, C₁₋₄alkoxy, phenyl or hydroxy; aC₅₋₆cycloalkylamino group, the cycloalkyl group being unsubstituted orsubstituted by one or two C₁₋₂alkyl groups; a phenylamino group, thephenyl ring being unsubstituted or substituted by one or two groupsselected from halogen, C₁₋₄alkyl, C₁₋₄alkoxy, hydroxy and phenoxy; or a5- or 6-membered ring containing one or two hetero atoms, in addition toN, O or S, which heterocyclic ring is unsubstittited or substituted byone or two C₁₋₄alkyl groups; or a group Z, where Z is Independentlyselected from

where p is 0 or an integer 1, 2, or 3, each R₂ is independently H;unsubstituted C₁₋₄alkyl or C₁₋₄alkyl monosubstituted by hydroxy,halogen, cyano or C₁₋₄alkoxy, each R₃ and R₄ is independently H;unsubstituted C₁₋₆alkyl; C₂₋₆alkyl monosubstituted by hydroxy or cyano;phenyl or phenyl-C₁₋₄alkyl, where the phenyl ring of the latter twogroups is unsubstituted or substituted by one to three groups selectedfrom chlorine, C₁₋₄alkyl, C₁₋₄alkoxy, unsubstituted C₅₋₆cycloalkyl orC₅₋₆cycloalkyl substituted by one to three C₁₋₄alkyl groups, or apyridinium ring, or R₃ and R₄ together with the nitrogen atom to whichthey are attached, form a 5- or 6-membered ring containing one to threehetero atoms (in addition to N, one or two further N, O or S), whichheterocyclic ring is unsubstituted or substituted by one or twoC₁₋₄alkyl groups, each R₅ and R₆ has independently one of the groups asdefined in R₃ and R₄, except hydrogen, R₇ is C₁₋₄alkyl or benzyl withthe exception that R₇ is not benzyl when R₅ and R₆ have one of thecyclic groups as defined in R₃ and R₄ or R₅, R₆ and R₇ together with thenitrogen atom to which they are attached, form a pyridinium ring whichis unsubstituted or substituted by one or two methyl groups, Q₁ isC₂₋₆alkylene; branched C₂₋₈alkylene; C₂₋₆alkylene substituted by one ortwo hydroxy groups; C₁₋₆alkylene-1,3-phenylene; orC₁₋₆alkylene-1,4-phenylene, Q₂ is C₂₋₈alkylene; branched C₂₋₈alkylene;C₃₋₆alkylene substituted by one or two hydroxy groups;C₁₋₆alkylene-1,3-phenylene; C₁₋₆alkylene-1,4-phenylene; 1,3- phenyleneor 1,4-phenylene, Q₃ is C₂₋₈alkylene, R₈ is H; unsubstituted C₁₋₆alkylor C₁₋₆alkyl monosubstituted by hydroxy, cyano, chlorine or phenyl, R₉is unsubstituted C₁₋₆alkyl or C₁₋₆alkyl monosubstituted by hydroxy,cyano or chlorine, and An^(θ) is a non-chromophoric anion, E is NH or adirect bond, m is 0 or 1, and if m is 1 the phenyl group is substitutedmeta or para, and DK is a radical of formula (a)

 wherein R₁₀ is SO₂—Y or —O—Y, where Y is a C₂₋₄-alkenyl group or aC₂₋₄alkyl group which is substituted by —CN, —OH, —OSO₃H, halogen or—NR₁₁R₁₂, wherein R₁₁ and R₁₂ are independently from one another H,C₁₋₄alkyl or substituted C₁₋₄alkyl, or R₁₁ and R₁₂ together with thenitrogen atom to which they are attached, form a 5- or 6-membered ringcontaining one to three hetero atoms (in addition to N, one or twofurther N, O or S), which heterocyclic ring is unsubstituted orsubstituted, R′₁₀ and R″₁₀ are independently from one another H;C₁₋₂alkyl; OC₁₋₂alkyl; —SO₃H; —OH or —CN; as well as their salts and/ormixtures thereof.
 2. A compound according to claim 1 where thesubstituted triazinyl radical is attached to the naphthol radical at the6 or 7 position.
 3. A compound according to claim 1 where R₁ is a R_(1a)where each R_(1a) is independently H; methyl; ethyl or 2-hydroxyethyl.4. A compound according to claim 1 where X₁ and X₂ are independentlyfrom each other mono(C₁₋₄alkyl) amino-radical; a di(C₁₋₄alkyl) aminoradical; a mono(C₁₋₄alkyl)- or di(C₁₋₄alkyl)-amino group in which eachalkyl group is independently monosubstituted by halogen, C₁₋₄alkoxy,phenyl or hydroxy; C₅₋₆cycloalkyl-amino group; C₅₋₆cycloalkyl-aminogroup in which the cycloalkyl group is substituted by one or twoC₁₋₂alkyl groups; a phenylamino group; a phenylamino group in which thephenyl ring is substituted by one or two groups selected from halogen,C₁₋₄alkyl, C₁₋₄alkoxy, hydroxy and phenoxy; a saturated 5- or 6-memberedring containing one or two hetero atoms; a saturated 5- or 6-memberedring containing one or two hetero atoms which heterocyclic ring issubstituted by one or two C₁₋₄alkyl groups.
 5. A compound according toclaim 1 where Z has the meaning Z_(a), wherein each Z_(a) isindependently a group selected from

in which p′is 0 or 1, R_(2b) is H: methyl or 2-hydroxyethyl, Q_(1b) isunsubstituted C₂₋₈alkylene; monohydroxy-substituted C₃₋₄alkylene;—(CH₂)₁₋₄-1,3- phenylene; —(CH₂)₁₋₄-1,4-phenylene; 1,3-phenylene or1,4-phenylene, each R_(2b) and Q_(3b) is a linear C₂₋₆alkylene group,each R_(3b) and R_(4b) is independently H; unsubstituted C₁₋₄alkyl or2-hydroxy-ethyl, or a pyridinium ring, each R_(5b) and R_(6b) isindependently unsubstituted C₁₋₄alkyl or 2-hydroxy-ethyl, R_(7b) isC₁₋₄alkyl or benzyl or R_(5b), R_(6b) and R_(7b) together with thenitrogen to which they are attached form a pyridinium ring which isunsubstituted or substituted by one or two methyl groups, R_(8b) is H;methyl; ethyl or 2-hydroxyethyl, R_(9b) is methyl; ethyl or2-hydroxyethyl, R₁₀ is in position 4, and An^(θ) is a non-chromophoricanion.
 6. A compound according to claim 1, where n is 1 and DK is aradical of formula (a) wherein R₁₀ is SO₂Y or —O—Y wherein Y is aC₂₋₄alkyl group which is substituted by —Cl, —OH or —OSO₃H, R′₁₀ andR″₁₀ are independently from one another H; C₁₋₂alkyl or OC₁₋₂alkyl, R₁₁and R₁₂ independently from each other are H; —CH₃ or —CH₂CH₃; R₁₃ is H:—CH₃ or —OCH₃, R₁₄ and R₁₅ independently from each other are —CH₃;—CH₂CH₃; —OCH₃; —OCH₂CH₃ or —SO₃H, R₁₆, R₁₇ and R₁₈ are independentlyfrom each other H; —NH₂; —OH; or —SO₃H, R₁₉ and R₂₀ are independentlyfrom each other H; —CH₃; halogen; C₁₋₂alkyl; or —OCH₃, R₂₁ and R₂₂ areindependently from each other H; —CH₃ or —CH₂CH₃, R₂₃ is H; —CH₃ or—CH₂CH₃, R₂₄ is H; —CH₃ or —OCH₃, R₂₅ and R₂₆ are independently fromeach other H; —CH₃ or —CH₂CH₃.
 7. A compound according to claim 1, whereDK is a radical of formula (a), wherein at the R₁₀ position, theheterocyclic ring formed by R₁₁, R₁₂, and the nitrogen atom to whichthey are attached is substituted by one or two C₁₋₄alkyl groups.